This non provisional application claims the benefit of French Application No. 04 52821 filed on Nov. 30, 2004 and U.S. Provisional Application No. 60/638,371 filed on Dec. 27, 2004.
The present invention relates to a method for manufacturing a cosmetic composition comprising the use of sulfamides and derivatives thereof in the field of skincare and for example as a skin moisturizer, to novel sulfamide derivatives and to cosmetic compositions containing them.
The stratum corneum, which forms the interface with the dehydrating external environment, serves for example to delay the excessive loss of water originating from the deeper layers of the epidermis. The stratum corneum also protects against mechanical attack and the passage of chemical products and foreign microorganisms. It also constitutes the first line of defence against UV radiation.
The stratum corneum, which is 10 μm thick, is composed of vertically stacked corneocytes surrounded with a matrix of lipid-enriched membranes. Thus, it is a two-compartment system that may be compared with a brick wall, composed of anuclear cells (the “bricks”) and of intercellular lamellar membranes (the “cement”).
Urea is one of the ingredients widely used in moisturizing formulations. However, it can greatly modify the skin barrier by increasing the transepidermal water loss (TWL), which significantly reduces the barrier function of the stratum corneum.
Glycerol, another reference active agent in this field, has the drawback of making formulations tacky when it is used at high concentration.
There is thus a need to find alternative solutions in the field of skin moisturization.
The inventors have discovered that certain sulfamide derivatives of general formula (I) described below may be good moisturizers and may have a beneficial effect in terms of elasticity on the stratum corneum.
Thus, in one exemplary embodiment, the present invention relates to a method for manufacturing a cosmetic composition comprising the use of compounds of general formula (I):
in which
R1, R2, R3 and R4 represent, independently of each other:
a hydrogen atom,
a (C1-C10)alkyl group, for example a (C1-C6)alkyl group and for example a (C1-C4)alkyl group, optionally substituted with 1 to 5 groups chosen from —OR5, —NR6R7 and —SiR8R9R10, in which optionally 1 to 3 carbon atoms of the said (C1-C10)alkyl group may be replaced, independently of each other, with a hetero atom chosen from a nitrogen atom, a sulfur atom, an oxygen atom, a silicon atom and a sulfonyl group (—SO2—) including, for example, the group —O—SO2—NR6R7, or alternatively
(R1 and R2) and/or (R3 and R4) may form, with the nitrogen that bears them, a 5- to 7-membered heterocycle optionally substituted with 1 to 4 hydroxyl groups and/or a group —NR6R7, the heterocycle being chosen for example from pyrrolidine, piperazine, morpholine, azepane, pyrazolidine, imidazolidine and oxazolidine, and also partially unsaturated homologues thereof, for example pyrrole, pyridine or pyrimidine derivatives, or alternatively
(R1 and R3) or (R2 and R4) may form, with the group —N—(SO2)—N— that bears them, a 5- to 9-membered heterocycle optionally substituted with 1 to 4 hydroxyl groups and/or a group NR6R7 and chosen for example from 1,2,5-thiadiazolidine, 1,2,6-thiadiazinane, 1,2,7-thiadiazepane, 1,2,8-thiadiazocane and 1,2,9-thiadiazonane 1,1-dioxides,
R5, R6 and R7 represent, independently of each other,
a hydrogen atom, or
a (C1-C6)alkyl group, and
R5 may also represent a group such that —OR5 represents a phosphate or sulfate group,
R8, R9 and R10 represent, independently of each other, a (C1-C6)alkyl group,
and also the cosmetically acceptable salts thereof, solvates thereof such as hydrates, and isomers thereof, for non-therapeutic skincare, and for example as moisturizers, for example at a non-alkaline pH.
In another exemplary embodiment, the present invention relates to a cosmetic composition comprising a compound of formula (I), in a physiologically acceptable medium, for example at a non-alkaline pH.
In another exemplary embodiment, the present invention relates to a cosmetic composition comprising a compound of formula (I) as described above, with the exclusion of N,N′-bis(2-hydroxyethyl)sulfamide, in a physiologically acceptable medium, for example at a non-alkaline pH.
In another exemplary embodiment, the present invention relates to a cosmetic composition comprising, in a physiologically acceptable medium, for example at a non-alkaline pH, a compound of formula (I) as described above also comprising at least one additive chosen from an oil, a fatty substance, a gelling agent, a filler, a UV-screening agent, an odour absorber and a dyestuff.
In another exemplary embodiment, the present invention relates to a cosmetic treatment process for non-therapeutic skincare and/or for making up the skin, characterized in that it comprises the application to the skin of at least one cosmetic composition according to the present invention comprising a compound of formula (I) as defined above.
The Compounds of General Formula (I)
In the context of the present invention, an exemplary embodiment is the method for manufacturing a cosmetic composition comprising the use of the compounds of general formula (I) in which
R1, R2, R3 and R4 represent, independently of each other:
a hydrogen atom,
a (2,2-dimethyldioxolane)methyl group,
a (C1-C10)alkyl group optionally substituted with 1 to 5 groups chosen from —OR5, —NR6R7 and —SiR8R9R10, or alternatively
(R1 and R3) or (R2 and R4) form, together with the —N—(SO2)—N— group that bears them, a 6- to 8-membered heterocycle chosen from 1,2,6-thiadiazinane, 1,2,7-thiadiazepane and 1,2,8-thiadiazonane 1,1-dioxides, optionally substituted with 1 to 3 hydroxyl groups,
R5 represents
a hydrogen atom,
a (C1-C4)alkyl group,
a group —SO2NRR′, or
a group —SiR8R9R10,
R6 and R7 represent, independently of each other:
a hydrogen atom, or
a (C1-C4)alkyl group,
R8, R9 and R10 represent, independently of each other, a (C1-C4)alkyl group, and
R and R′ represent, independently of each other, a hydrogen atom or a (C1-C4) alkyl group,
and also the cosmetically acceptable salts thereof, solvates thereof such as hydrates and isomers thereof, for non-therapeutic skincare, and for example as moisturizers, for example at a non-alkaline pH.
These compounds of formula (I) will be referred to hereinbelow as “compounds A”, for reasons of simplicity.
Another exemplary embodiment is the method for manufacturing a cosmetic composition comprising the use of the compounds of general formula (I) in which
R1, R2, R3 and R4 represent, independently of each other:
a hydrogen atom,
a (C1-C6)alkyl group optionally substituted with 1 to 5 hydroxyl groups, 1 or 2 —SiMe3 groups or with a group —O—SO2NRR′, or alternatively
(R1 and R3) represent a hydrogen atom and (R2 and R4) together form, with the —N—(SO2)—N— group that bears them, a 1,2,7-thiadiazepane 1,1-dioxide group optionally substituted with 1 or 2 hydroxyl groups or a 1,2,6-thiadiazinane 1,1-dioxide group optionally substituted with 1 or 2 hydroxyl groups,
R and R′ represent, independently of each other:
a hydrogen atom, or
a (C1-C4)alkyl group,
and also the cosmetically acceptable salts thereof, solvates thereof such as hydrates, and isomers thereof, for non-therapeutic skincare, and for example as moisturizers, for example at a non-alkaline pH.
These compounds of formula (I) will be referred to hereinbelow as “compounds B”, for reasons of simplicity.
In the context of the present invention, the term “alkyl” means a linear or branched, saturated or unsaturated, cyclic or non-cyclic hydrocarbon-based chain. Among the alkyl groups that are suitable for use in the invention, mention may be made for example of the methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, —CH2-t-butyl, pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, heptyl, octyl, nonyl, decyl, norbornyl and adamantyl groups.
Among the (C1-C10)alkyl groups in which 1 to 3 carbon atoms may be replaced with a hetero atom, mention may be made of the (2,2-dimethyldioxolane)methyl group.
In the context of the present invention, the term “non-alkaline pH” means a pH of between 4 and 7 and for example between 5 and 6.
Some of the compounds of formula (I) are known. The following documents describe some of them and give useful indications regarding the modes of synthesis described below.    L. F. Audrieth, M. Sveda, H. Sisler, M. Josetta Butler, Chemical Review, 1940, 26, 49-94,    Paquin, Angewante Chemie, 1948, 60, 11/12, 316-320,    K. Sprott, P. Hanson, Journal of Organic Chemistry, 2000, 65, 7913-7918,    M. McReynolds, K. Sprott, P. Hanson, Organic Letters, 2002, 4, 26, 4673-4676,    H. Preuschhof, H-U. Heyne, Organic Syntheses, Collective volume 6, 78, step 1,    J. M. Dougherty, D. A. Probst, R. E. Robinson, J. D. Moore, T. A. Klein, K. A. Snelgrove, P. R. Hanson, Tetrahedron, 2000, 56, 9781-9790,    G. Dewynter, M. Abdaoui, L. Toupet, J-L. Montero, Tetrahedron Letters, 1997, 38, 8691-8694, and    Y. Masui, H. Watanabe, T. Masui, Tetrahedron Letters, 2004, 45, 1853-1856, G. M. Atkins, E. M. Burgess, Journal of the American Chemical Society, 1968, 90, 4744-4745.Compounds According to the Invention and Mode of Preparation Thereof.
The compounds of formulae (II), (III) and (N) defined below also form part of the invention.
According to one exemplary embodiment, the invention is related to compounds of formula (II)
in which:
R12 represents a hydrogen atom, a group —SiR8R9R10, a (C1-C9)alkyl group optionally substituted with 1 to 5 groups chosen from —OR5, —NR6R7 and —SiR8R9R10, in which optionally 1 to 3 carbon atoms of the said (C1-C9)alkyl group may be replaced, independently of each other, with a hetero atom chosen from a nitrogen atom, a sulfur atom, an oxygen atom and a silicon atom or a sulfonyl group (—SO2—),
R11 represents a hydrogen atom, a (C1-C6)alkyl group optionally substituted with 1 to 5 groups chosen from —OR5 and/or —SiR8R9R10 or optionally with a group —OSO2—NRR′,
R5, R6, R7, R8, R9, R10, R and R′ being as defined above for the compounds A and the compounds B of formula (I), and also the solvates thereof such as hydrates, salts thereof and isomers thereof.
In one exemplary embodiment, the compounds of formula (II) are those in which:
R12 represents a hydrogen atom, an —SiMe3 group or a (C1-C6)alkyl group optionally substituted with 1 to 5 hydroxyl groups, 1 or 2 —SiMe3 groups or with an —O—SO2NH2 group,
R11 represents a hydrogen atom or a (C1-C6)alkyl group optionally substituted with 1 or 2 groups chosen from —OR5 and —SiMe3,
R5, R8, R9 and R10 being as defined above for the compounds A and the compounds B of formula (I), and also the solvates thereof such as the hydrates, salts thereof and isomers thereof.
In one exemplary embodiment, the compounds of formula (II) are those in which:
R12 represents a hydrogen atom, an —SiMe3 group or a (C1-C6)alkyl group optionally substituted with a hydroxyl group,
R11 represents a hydrogen atom or a (C1-C6)alkyl group optionally substituted with 1 or 2 hydroxyl groups, and
R8, R9 and R10 each represent a methyl group, and also solvates thereof such as hydrates, salts thereof and isomers thereof.
According to another exemplary embodiment, the invention relates to the compounds of formula (III)
in which:
R13 represents a (C1-C9)alkyl substituted with 1 to 5 groups chosen from —OR5 and —NR6R7, or a group —O—SO2NRR′,
R13′ represents a hydrogen atom or a (C1-C4)alkyl group, and
R5, R6 and R7 are as defined above for the compounds A and the compounds B of formula (I),
R and R′ being as defined above for the compounds A and the compounds B of formula (I),
and also solvates thereof such as hydrates, salts thereof and isomers thereof.
In one exemplary embodiment, the invention relates to the compounds of formula (II) in which R13 represents a (C1-C9)alkyl substituted with 1 to 5 groups chosen from —OR5 and a group —O—SO2NRR′, R5 representing a hydrogen atom, a (C2-C4)alkyl a group —SO2NRR′, or a group —SiR8R9R10 with R8, R9, R10, R and R′ being as defined above for the compounds A and the compounds B of formula (I).
In one exemplary embodiment, the compounds of formula (III) are those in which:
R13 represents a (C1-C9)alkyl group substituted with 1 to 5 hydroxyl group(s) or with an —O—SO2NH2 group, and
R13′ represents a hydrogen atom or a methyl group, and also solvates thereof such as hydrates, salts thereof and isomers thereof.
According to yet another exemplary embodiment, the invention relates to the compounds of formula (IV)
in which:
X and X′ take, independently of each other, the meaning of R5 as defined above for the compounds of formula (I) and Y and Y′ represent, independently of each other, a hydrogen atom, a group —CH2Z, in which Z represents an amine group or a group —NR6R7 or —OR5, or alternatively
at least one of the groups

forms, independently of each other, a dimethyldioxolane group, or alternatively:
X and X′ are hydrogen atoms and Y and Y′ together form a covalent bond,
R1, R3, R5, R6 and R7 take the same meaning as that defined for the compounds of formula (I), and X, X′, Y and Y′ advantageously do not simultaneously represent a hydrogen atom.
A subject of the invention is, for example, the compounds of formula (IV) in which Y and Y′ are not simultaneously a hydrogen atom when X and X′ simultaneously represent a —CH3 group.
According to one exemplary embodiment, the compounds of formula (IV) are those in which:
X and X′ are hydrogen atoms and Y and Y′ represent a group
—CH2OR5, or alternatively
at least one of the groups
forms a dimethyldioxolane group, or alternatively
X and X′ are hydrogen atoms and Y and Y′ together form a covalent bond, and
R1, R3 and R5 take the same meaning as that defined by the compounds of formula (I).
In one exemplary embodiment, the compounds of formula (IV) are those in which:
X and X′ are hydrogen atoms and Y and Y′ represent a —CH2OH group, or alternatively
X and X′ are hydrogen atoms and Y and Y′ together form a covalent bond, and
R1 and R3 represent a hydrogen atom or a (C1-C6)alkyl group.
The salts that are acceptable for the non-therapeutic use of the compounds described in the present invention include the conventional non-toxic salts of the said compounds, such as those formed from organic or mineral acids. Examples that may be mentioned include the salts of mineral acids, such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydriodic acid, phosphoric acid or boric acid. Mention may also be made of the salts of organic acids, which may comprise one or more carboxylic, sulfonic or phosphonic acid groups. They may be linear, branched or cyclic aliphatic acids or alternatively aromatic acids. These acids may also comprise one or more hetero atoms chosen from O and N, for example in the form of hydroxyl groups. Mention may be made for example of propionic acid, acetic acid, terephthalic acid, citric acid and tartaric acid.
When the compound of formula (I) comprises an acid group, the neutralization of the acid group(s) may be performed with a mineral base, such as LiOH, NaOH, KOH, Ca(OH)2, NH4OH, Mg(OH)2 or Zn(OH)2; or with an organic base such as a primary, secondary or tertiary alkylamine, for example triethylamine or butylamine. This primary, secondary or tertiary alkylamine may comprise one or more nitrogen and/or oxygen atoms and may thus comprise, for example, one or more alcohol functions; mention may be made especially of 2-amino-2-methylpropanol, triethanolamine, 2-dimethylaminopropanol and 2-amino-2-(hydroxymethyl)-1,3-propanediol. Mention may also be made of lysine or 3-(dimethylamino)propyl amine.
The solvates that are acceptable for the non-therapeutic use of the compounds described in the present invention include conventional solvates such as those formed during the final step of preparation of the said compounds, due to the presence of solvents. Examples that may be mentioned include the solvates due to the presence of water or of linear or branched alcohols, for instance ethanol or isopropanol.
The compounds of formula (I) may be prepared according to techniques that are well known to those skilled in the art, for example according to a scheme 1 described below.
The standard modes for obtaining sulfamide are performed starting with sulfuryl chloride.
The amines (or diamines) chosen to give the compounds of formula (I) may be reacted (sequentially for the dissymmetric compounds) with an electrophilic source of SO2, such as sulfamide H2NSO2NH2, sulfuryl chloride SO2Cl2, or sulfonylbis(2-oxazolidine) in a suitable solvent (for example, respectively, acetonitrile, pyridine or dimethylformamide for sulfamide, or, for example, dichloromethane or tetrahydrofuran for sulfuryl chloride), for example at a temperature ranging from 0 to 140° C. in the presence or absence of a base, for instance diazabicycloundecene, triethylamine or pyridine.

The methods for synthesizing the novel compounds of formulae (II), (III) and (IV), respectively, are detailed below.
The compounds of formula (II) may be prepared according to scheme 2 below:

The compounds (II) may be obtained in two ways:
either using sulfamide by reacting one mole of silyl amine of formula (VI), for example in a polar solvent such as acetonitrile, dimethylformamide or pyridine, for example at a temperature of between 0 and 140° C. in the presence or absence of a catalytic amount of base, for instance diazabicycloundecene, to give the compounds of formula (V), followed by a second addition of one mole of amine R11NH2, for example under similar conditions,
or using chlorosulfonyl isocyanate by performing a sequential addition of tert-butanol and of silyl amine of formula (VII), for example, in a solvent such as dichloromethane or ethyl acetate, for example between 0 and 20° C. in the presence of a base, for instance triethylamine or pyridine, in order to obtain a dissymmetric sulfamide in which the NH2 group, protected in the form of tert-butoxycarbonyl, is released by means of an acidic treatment with, for example, hydrochloric acid or trifluoroacetic acid; compound (II) may then be formed via addition of one mole of amine of formula R11NH2 in a polar solvent such as acetonitrile, dimethylformamide or pyridine, for example at a temperature of between 0 and 140° C. and in the presence or absence of a catalytic amount of base, for instance diazabicycloundecene.
The compounds of formula (III) may be prepared according to scheme 3 below:

Chlorosulfonyl isocyanate is sequentially reacted with one mole of tert-butanol, followed by one mole of amine of formula (IX) in the presence of a base such as triethylamine or pyridine, for example in a solvent such as dichloromethane or ethyl acetate, for example at a temperature of between 0 and 20° C. The N-protected compound of formula (VIII) in tert-butoxycarbonyl form is then deprotected in acidic medium with, for example, hydrochloric acid or trifluoroacetic acid, for example at room temperature, to give the compounds of formula (III).
The compounds of formula (IV) may be prepared according to scheme 4, which is a particular form of scheme 1:

The amines (or diamines) of respective formulae (X) and (XI) chosen to give the compounds of formula (IV) are reacted (sequentially for the dissymmetric compounds) with an electrophilic source of SO2, such as sulfamide H2NSO2NH2, sulfuryl chloride SO2Cl2, or sulfonylbis(2-oxazolidine), in a suitable solvent (for example, respectively, acetonitrile, pyridine or dimethylformamide for sulfamide, or, for example, dichloromethane or tetrahydrofuran for sulfuryl chloride), for example at a temperature ranging from 0 to 140° C. in the presence or absence of a base, for instance diazabicycloundecene, triethylamine or pyridine.
The table below collates the compounds that may preferably be used in the context of the present invention.
TABLE 1No.Chemical nameFormula1Sulfamide 2N-(2-hydroxyethyl)sulfamide 3N-(3-hydroxypropyl)sulfamide 4N-(2,3-dihydroxypropyl)sulfamide 5N-(4-hydroxybutyl)sulfamide 6N-(2,3,4,5,6-penta- hydroxyhexyl)sulfamide 7N-Methyl-N-(2,3,4,5,6-penta- hydroxyhexyl)sulfamide 8N-[trimethylsilylmethyl]sulfamide 9N-[bis(trimethylsilyl)methyl]sulfamide 10N,N″-bis(hydroxyethyl)sulfamide 11N,N″-bis(hydroxypropyl)sulfamide 12N,N″-bis(hydroxybutyl)sulfamide 13N,N″-bis (2,3-dihydroxy- propyl)sulfamide 14N,N″-bis[(2,2-dimethyl-1,3-dioxolan- 4-yl)methyl]sulfamide 15N-[bis(trimethylsilyl)methyl]-N″-(2- hydroxyethyl)sulfamide 16N-[(trimethylsilyl)methyl]-N″-(2- hydroxyethyl)sulfamide 172-[(aminosulfonyl)amino]ethyl sulfamate 183-[(aminosulfonyl)amino]propyl sulfamate 19(+/−) 1,2,7-thiadiazepane-4,5-diol 1,1- dioxideCosmetic Formulations
In one exemplary embodiment, the present invention relates to a cosmetic composition comprising a compound of formula (I) as described above, with the exclusion of N,N′-bis(2-hydroxyethyl)sulfamide, in a physiologically acceptable medium, for example at a non-alkaline pH.
In one exemplary embodiment, the present invention relate to a cosmetic composition comprising, in a physiologically acceptable medium, for example at a non-alkaline pH, a compound of formula (I) as described above also comprising at least one additive chosen from an oil, a fatty substance, a gelling agent, a filler, a UV-screening agent, an odour absorber and a dyestuff.
These cosmetic compositions in which the compounds (I), (II), (III) or (IV) may be used are useful for non-therapeutic skincare and/or for making up the skin. They are useful for example for moisturizing the skin.
They may show their efficacy as a non-therapeutic, i.e. a preventive, skin maintenance treatment. They may also be used as a non-therapeutic skin treatment after the appearance of skin moisturization disorders.
In this second case, this appearance of skin moisturization disorders may be for example independent of irritation caused by the placing in contact of the skin with a bleaching agent, for example a chlorinated bleaching agent, for example based on hypochlorite.
In addition, the said cosmetic compositions may be for example not used for hygiene, purposes, and for example they preferably do not contain any detergent.
Finally, the cosmetic compositions of the invention may be for example formulated under non-alkaline conditions, for example at a pH close to that of the skin, for example at a pH of between 5 and 6.
The compounds of formula (I), (II), (III) or (IV) may be present in the cosmetic compositions in contents ranging from 0.01% to 20%, for example from 0.01% to 15% and for example from 0.1% to 10% by weight relative to the total weight of the cosmetic composition.
The compositions used according to the invention contain a physiologically acceptable medium, i.e. a medium that is compatible with skin tissues such as the skin and the scalp. This physiologically acceptable medium may consist for example of water and optionally of a physiologically acceptable organic solvent chosen, for example, from lower alcohols containing from 1 to 8 carbon atoms and for example from 1 to 6 carbon atoms, for instance ethanol, isopropanol, propanol or butanol; polyethylene glycols containing from 6 to 80 ethylene oxide units and polyols, for instance propylene glycol, isoprene glycol, butylene glycol, glycerol and sorbitol.
The compositions according to the invention may be in any galenical form conventionally used for topical application, and for example in the form of aqueous or aqueous-alcoholic solutions, oil-in-water (O/W) emulsions, water-in-oil (W/O) emulsions or multiple emulsions (triple: W/O/W or O/W/O), aqueous gels, or dispersions of a fatty phase in an aqueous phase by means of spherules, these spherules possibly being polymer nanoparticles such as nanospheres and nanocapsules or lipid vesicles of ionic and/or nonionic type (liposomes, niosomes or oleosomes). These compositions are prepared according to the usual methods.
In addition, the compositions used according to the invention may be more or less fluid and may have the appearance of a white or coloured cream, a pomade, a milk, a lotion, a serum, a paste or a mousse. They may be optionally applied to the skin in aerosol form. They may also be in solid form, for example in the form of a stick.
When the composition used according to the invention comprises an oily phase, it contains for example at least one oil. It may also contain other fatty substances.
As examples of oils that may be used in the composition of the invention, mention may be made of:
hydrocarbon-based oils of animal origin, such as perhydrosqualene;
hydrocarbon-based oils of plant origin, such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for instance heptanoic or octanoic acid triglycerides or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stéarineries Dubois or those sold under the names “Miglyol 810”, “812” and “818” by the company Dynamit Nobel, jojoba oil or shea butter oil;
synthetic esters and synthetic ethers, for example of fatty acids, for instance oils of formulae R1COOR2 and R1OR2 in which R1 represents the fatty acid residue containing from 8 to 29 carbon atoms and R2 represents a branched or unbranched hydrocarbon-based chain containing from 3 to 30 carbon atoms, such as, for example, purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyl-dodecyl stearate, 2-octyldodecyl erucate or isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate and fatty alkyl heptanoates, octanoates and decanoates; polyol esters, for instance propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters, for instance pentaerythrityl tetraisostearate;
linear or branched hydrocarbons of mineral or synthetic origin, such as volatile or non-volatile paraffin oils, and derivatives thereof, petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam oil;
fatty alcohols containing from 8 to 26 carbon atoms, for instance cetyl alcohol, stearyl alcohol and the mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol;
partially hydrocarbon-based and/or partially silicone-based fluoro oils, for instance those described in document JP-A-2 295 912;
silicone oils, for instance volatile or non-volatile polymethylsiloxanes (PDMSs) containing a linear or cyclic silicone chain, that are liquid or pasty at room temperature, for example cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, that are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyl-trisiloxanes, 2-phenylethyltrimethyl siloxysilicates and polymethylphenylsiloxanes;
mixtures thereof.
In the list of oils mentioned above, the expression “hydrocarbon-based oil” means any oil mainly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and/or alcohol groups.
The other fatty substances that may be present in the oily phase are, for example, fatty acids containing from 8 to 30 carbon atoms, for instance stearic acid, lauric acid, palmitic acid and oleic acid; waxes, for instance lanolin, beeswax, carnauba wax or candelilla wax, paraffin wax, lignite wax or microcrystalline waxes, ceresin or ozokerite, synthetic waxes such as polyethylene waxes, Fischer-Tropsch waxes; silicone resins such as trifluoromethyl-C1-4-alkyl dimethicone and trifluoropropyl dimethicone; and silicone elastomers, for instance the products sold under the name “KSG” by the company Shin-Etsu, under the name “Trefil”, “BY29” or “EPSX” by the company Dow Corning, or under the name “Gransil” by the company Grant Industries.
These fatty substances may be chosen in a varied manner by a person skilled in the art so as to prepare a composition having the desired properties, for example in terms of consistency or texture.
According to one exemplary embodiment of the invention, the composition according to the invention is a water-in-oil (W/O) or oil-in-water (O/W) emulsion. The proportion of the oily phase of the emulsion may range from 5% to 80% by weight and for example from 5% to 50% by weight relative to the total weight of the composition.
The emulsions may contain at least one emulsifier chosen from amphoteric, anionic, cationic and nonionic emulsifiers, used alone or as a mixture, and optionally a co-emulsifier. The emulsifiers are chosen in a suitable manner depending on the emulsion to be obtained (W/O or O/W). The emulsifier and the co-emulsifier may be present in the composition in a proportion that may range, for example, from 0.3% to 30% by weight and for example from 0.5% to 20% by weight relative to the total weight of the composition.
Examples of emulsifiers that may be mentioned for the W/O emulsions include dimethicone copolyols such as the mixture of cyclomethicone and of dimethicone copolyol, sold under the name “DC 5225 C” by the company Dow Corning, and alkyldimethicone copolyols, such as the laurylmethicone copolyol sold under the name “Dow Corning 5200 Formulation Aid” by the company Dow Corning, and the cetyldimethicone copolyol sold under the name “Abil EM 90®” by the company Goldschmidt. Surfactants for W/O emulsions that may also be used include a crosslinked elastomeric solid organopolysiloxane comprising at least one oxyalkylene group, such as those obtained according to the procedure of Examples 3, 4 and 8 of document U.S. Pat. No. 5,412,004 and of the examples of document U.S. Pat. No. 5,811,487, for example the product of Example 3 (synthesis example) of U.S. Pat. No. 5,412,004, and such as the product sold under the reference KSG 21 by the company Shin-Etsu.
Examples of emulsifiers that may be mentioned for the 0/W emulsions include nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fatty acid esters of sorbitan; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty acid esters; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohol ethers; sugar esters, for instance sucrose stearate; and mixtures thereof, such as the mixture of glyceryl stearate and of PEG-40 stearate.
In a known manner, the cosmetic or dermatological composition of the invention may also contain adjuvants that are common in cosmetics or dermatology, such as gelling agents, film-forming polymers, preserving agents, solvents, fragrances, fillers, UV-screening agents, bactericides, odour absorbers, dyestuffs, plant extracts and salts. The amounts of these various adjuvants are those conventionally used in the field under consideration, for example from 0.01% to 20% of the total weight of the composition. Depending on their nature, these adjuvants may be introduced into the fatty phase and/or into the aqueous phase.
The compounds of formulae (I), (II), (III) and (IV) may be combined together, or with other skin moisturizers not in accordance with formula (I) and/or with at least one other cosmetic active agent.
Additional cosmetic active agents that may for example be mentioned include active agents acting on the barrier function of the skin, active agents that promote skin moisturization and desquamating agents.
The term “desquamating agent” means any compound capable of acting:
either directly on desquamation by promoting exfoliation, such as β-hydroxy acids, in particular salicylic acid and its derivatives (including 5-n-octanoylsalicylic acid); α-hydroxy acids, such as glycolic acid, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid; urea; gentisic acid; oligofucoses; cinnamic acid; extract of Saphora japonica; resveratrol;
or on the enzymes involved in the desquamation or degradation of corneodesmosomes, such as glycosidases, stratum corneum chymotryptic enzyme (SCCE), or even other proteases (trypsin, chymotrypsin-like). Mention may be made of agents for chelating mineral salts: EDTA; N-acyl-N,N′,N′-ethylenediaminetriacetic acid; aminosulfonic compounds and for example (N-2-hydroxyethylpiperazine-N′-2-ethane)sulfonic acid (HEPES); 2-oxothiazolidine-4-carboxylic acid (procysteine) derivatives; α-amino acid derivatives of the type such as glycine (as described in EP-0 852 949 and sodium methylglycinediacetate sold by BASF under the trade name “Trilon M”); honey; sugar derivatives such as O-octanoyl-6-D-maltose and N-acetylglucosamine.
Among the active agents acting on the barrier function of the skin, or that promote skin moisturization, mention may be made of:
either a compound acting on the barrier function, in order to keep the stratum corneum moisturized, or an occlusive compound, for example ceramides, sphingoid-based compounds, lecithins, glycosphingolipids, phospholipids, cholesterol and its derivatives, phytosterols (stigmasterol, β-sitosterol or campesterol), essential fatty acids, 1,2-diacylglycerol, 4-chromanone, pentacyclic triterpenes such as ursolic acid, petroleum jelly and lanolin;
or a compound that directly increases the water content of the stratum corneum, such as threalose and its derivatives, hyaluronic acid and its derivatives, glycerol, pentanediol, sodium pidolate, serine, xylitol, sodium lactate, polyglyceryl acrylate, ectoin and its derivatives, chitosan, oligosaccharides and polysaccharides, cyclic carbonates, N-lauroylpyrrolidonecarboxylic acid and N-α-benzoyl-L-arginine;
or a compound that activates the sebaceous glands, such as steroid derivatives (including DHEA) and vitamin D and its derivatives.
The composition may be in the form of a non-therapeutic care and/or makeup product, and also in the form of a lip balm.
In yet one exemplary embodiment, the invention relates to a cosmetic treatment process for non-therapeutic skincare and/or for making up the skin, characterized in that it comprises the application to the skin of at least one cosmetic composition according to the present invention comprising at least one compound of formula (I), (II), (III) or (IV) as defined above or a mixture thereof in all proportions.
Among the applications of makeup type that may be envisaged by means of the cosmetic treatment process, mention may be made for example of foundations, makeup rouges, eyeshadows, concealer products and body makeup products.
In another exemplary embodiment, the invention relates to a method for preparing a dermatological composition for moisturizing the skin and for example for treating dryness of the skin or for treating dry skin comprising the use of a compound of formula (I), (II), (III) or (IV) as defined above, or a mixture thereof.
The examples below illustrate the invention without, however, limiting its scope.
The elemental analyses and the NMR spectra confirm the structures of the products obtained.
The numbers given in parentheses in the example titles correspond to those in Table 1 given above.